It is well known that phyllosilicates, such as smectite clays, e.g., sodium montmorillonite and calcium montmorillonite, can be treated with organic molecules, such as organic ammonium ions, to intercalate the organic molecules between adjacent, planar silicate layers, for bonding the organic molecules with a polymer, for intercalation of the polymer between the layers, thereby substantially increasing the interlayer (interlaminar) spacing between the adjacent silicate layers. The thus-treated, intercalated phyllosilicates, having interlayer spacings of at least about 10-20 .ANG. and up to about 100 Angstroms, then can be exfoliated, e.g., the silicate layers are separated, e.g., mechanically, by high shear mixing. The individual silicate layers, when admixed with a matrix polymer, before, after or during the polymerization of the matrix polymer, e.g., a polyamide--see U.S. Pat. Nos. 4,739,007; 4,810,734; and 5,385,776--have been found to substantially improve one or more properties of the polymer, such as mechanical strength and/or high temperature characteristics.
Exemplary prior art composites, also called "nanocomposites", are disclosed in published PCT disclosure of Allied Signal, Inc. WO 93/04118 and U.S. Pat. No. 5,385,776, disclosing the admixture of individual platelet particles derived from intercalated layered silicate materials, with a polymer to form a polymer matrix having one or more properties of the matrix polymer improved by the addition of the exfoliated intercalate. As disclosed in WO 93/04118, the intercalate is formed (the interlayer spacing between adjacent silicate platelets is increased) by adsorption of a silane coupling agent or an onium cation, such as a quaternary ammonium compound, having a reactive group which is compatible with the matrix polymer. Such quaternary ammonium cations are well known to convert a highly hydrophilic clay, such as sodium or calcium montmorillonite, into an organophilic clay capable of sorbing organic molecules. A publication that discloses direct intercalation (without solvent) of polystyrene and poly(ethylene oxide) in organically modified silicates is Synthesis and Properties of Two-Dimensional Nanostructures by Direct Intercalation of Polymer Melts in Layered Silicates, Richard A. Vaia, et al., Chem. Mater., 5:1694-1696(1993). Also as disclosed in Adv. Materials, 7, No. 2: (1985), pp, 154-156, New Polymer Electrolyte Nanocomposites: Melt Intercalation of Poly(Ethylene Oxide) in Mica-Type Silicates, Richard A. Vaia, et al., poly(ethylene oxide) can be intercalated directly into Na-montmorillonite and Li-montmorillonite by heating to 80.degree. C. for 2-6 hours to achieve a d-spacing of 17.7 .ANG.. The intercalation is accompanied by displacing water molecules, disposed between the clay platelets, with polymer molecules. Apparently, however, the intercalated material could not be exfoliated and was tested in pellet form. It was quite surprising to one of the authors of these articles that exfoliated material could be manufactured in accordance with the present invention.
Previous attempts have been made to intercalate polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and poly(ethylene oxide) (PEO) between montmorillonite clay platelets with little success. As described in Levy, et al., Interlayer Adsorption of Polyvinylpyrrolidone on Montmorillonite, Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975, pages 442-450, attempts were made to sorb PVP (40,000 average M.W.) between monoionic montmorillonite clay platelets (Na, K, Ca and Mg) by successive washes with absolute ethanol, and then attempting to sorb the PVP by contact with 1% PVP/ethanol/water solutions, with varying amounts of water, via replacing the ethanol solvent molecules that were sorbed in washing (to expand the platelets to about 17.7 .ANG.). Only the sodium montmorillonite had expanded beyond a 20 .ANG. basal spacing (e.g., 26 .ANG. and 32 .ANG.), at 5.sup.+ % H.sub.2 O, after contact with the PVP/ethanol/H.sub.2 O solution. It was concluded that the ethanol was needed to initially increase the basal spacing for later sorption of PVP, and that water did not directly affect the sorption of PVP between the clay platelets (Table II, page 445), except for sodium montmorillonite. The sorption was time consuming and difficult and met with little success.
Further, as described in Greenland, Adsorption of Polyvinyl Alcohols by Montmorillonite, Journal of Colloid Sciences, Vol. 18, pages 647-664 (1963), polyvinyl alcohols containing 12% residual acetyl groups could increase the basal spacing by only about 10 .ANG. due to the sorbed polyvinyl alcohol (PVA). As the concentration of polymer in the intercalant polymer-containing solution was increased from 0.25% to 4%, the amount of polymer sorbed was substantially reduced, indicating that sorption might only be effective at polymer concentrations in the intercalant polymer-containing composition on the order of 1% by weight polymer, or less. Such a dilute process for intercalation of polymer into layered materials would be exceptionally costly in drying the intercalated layered materials for separation of intercalate from the polymer carrier, e.g., water, and, therefore, apparently no further work was accomplished toward commercialization.
In accordance with one embodiment of the present invention, intercalates are prepared by contacting a phyllosilicate with a monomeric, oligomeric or polymeric organic intercalant compound selected from (a) a compound having a long chain alkyl radical (C.sub.6 + alkyl) or (b) an aromatic ring-containing compound, both (a) and (b) intercalant compounds having a free matrix polymer-compatible, reactive functionality covalently bonded to the C.sub.6 + alkyl or aromatic ring. The matrix polymer-compatible functionality is a moiety, for example, selected from the group consisting of an amine; a carboxylic acid or a carboxylic acid metal salt; a polycarboxylic acid or salt thereof; a hydroxyl; a polyhydroxyl; a carbonyl; an amide; an ether; an ester; a lactam; an aldehyde; a ketone; a lactone; an anhydride; a nitrile; an n-alkyl halide; a pyridine; a pyrrolidone; a free carbon to carbon double bond or triple bond ##STR2##
or --C.dbd.C--; and mixtures thereof. The intercalant compound has an electrostatic functionality on the other end of the molecule that provides for complexing to cations, e.g., Na.sup.+ cations, on the inner surfaces of the layered material platelets. Exemplary of such electrostatic functionalities include a hydroxyl; a polyhydroxyl; a carbonyl, such as carboxylic acids, and salts thereof; a polycarboxylic acid and salts thereof; an aldehyde; a ketone; an amine; an amide; an ether; an ester; a lactam; a lactone; an anhydride; a nitrile; a n-alkyl halide; a pyridine; a pyrrolidone; and mixtures thereof.
In accordance with an important feature of the present invention, best results are achieved by mixing the layered material with a polar monomeric, oligomeric or polymeric organic intercalant compound, having a C.sub.6 + alkyl group and/or an aromatic ring. The intercalant compounds include a matrix polymer-compatible end group covalently bonded to one end of the C.sub.6 + alkyl group or aromatic ring. The matrix polymer-compatible intercalant includes a C.sub.6 + alkyl group and/or aromatic ring having a free functional group covalently bonded to the molecule, such as a functionality selected from the group consisting of an amine, a carboxylic acid, a metal salt of a carboxylic acid, a hydroxyl; a polyhydroxyl; a carbonyl; an amide; an ether; an ester; a lactam; a polycarboxylic acid or salt thereof; an aldehyde; a ketone; a lactone; an anhydride; a nitrile; an n-alkyl halide; a pyridine; a pyrrolidone; an unsaturated carbon to carbon bond, such as ##STR3##
or --C.dbd.C--; and mixtures thereof. The intercalant compound also has an electrostatic complexing functionality on the other end of the intercalant molecule that electrostatically complexes with interlayer cations on the interlayer platelet surfaces.
The intercalant compound is intercalated into the layered material by contacting the layered material with an intercalating composition containing the intercalant compound in a concentration of at least about 2%, preferably at least about 5% by weight long chain alkyl and/or aromatic ring-containing intercalant compound, more preferably at least about 10% by weight long chain alkyl or aromatic ring-containing intercalant compound, and most preferably about 30% to about 80% by weight, based on the weight of long chain (C.sub.6 +) alkyl or aromatic ring-containing intercalant compound and carrier (e.g., water, with or without an organic solvent for the long chain alkyl or aromatic ring-containing intercalant compound) to achieve better sorption of the organic intercalant compound between the platelets of the layered material. Regardless of the concentration of intercalant compound in the intercalant carrier, the intercalating composition should have a long chain and/or aromatic ring-containing intercalant compound:layered material weight ratio of at least 1:20, preferably at least 1:10, more preferably at least 1:5, to achieve efficient electrostatic complexing of one end of the intercalant compound with an inner surface of a platelet of the layered material. The long chain (C.sub.6 + alkyl) and/or aromatic ring-containing intercalant compound sorbed between and complexed with the silicate platelets causes surprising separation or added spacing between adjacent silicate platelets.
For simplicity of description, the above-described (a) C.sub.6 + alkyl monomeric, oligomeric, or polymeric intercalant compounds and (b) aromatic ring-containing monomeric, oligomeric, or polymeric intercalant compounds, wherein both (a) and (b) intercalant compounds have at least one phyllosilicate platelet-complexing molecule end that has an electrostatic attraction for, and complexes with, interlayer cations of the layered material, and another free functionality, somewhere along the molecule or at the molecule end, that has a matrix polymer-compatible and polymer-reactive functional group, are hereinafter called the "intercalant" or "surface modifier" or "intercalant surface modifier". The intercalant will be sorbed sufficiently to increase the interlayer spacing of the phyllosilicate in the range of about 5 .ANG. to about 100 .ANG., preferably at least about 10 .ANG. for easier and more complete exfoliation, in a commercially viable process, regardless of the particular layered material, e.g., phyllosilicate, or intercalant.
In accordance with the present invention, it has been found that a phyllosilicate, such as a smectite clay, can be intercalated sufficiently for subsequent exfoliation by sorption of the above-described intercalant compounds (having an alkyl group of at least 6 carbon atoms or an aromatic ring; an electrostatic functionality on one end of the molecule to provide bonding (complexing) between the electrostatic functionality of one or two intercalant molecules and the Na.sup.+ or other cations of the inner surfaces of the platelets of the layered material, e.g., phyllosilicate; and a matrix polymer-compatible and reactive functionality extending from the intercalant molecule or on a free end thereof, without prior sorption of an onium ion or silane coupling agent. Sorption and metal cation attraction or bonding between two electrostatic end groups of the intercalant molecules and the interlayer cations of the phyllosilicate; or the bonding between the interlayer cations in hexagonal or pseudohexagonal rings of the smectite platelet layers and an intercalant aromatic ring structure, is provided by a mechanism selected from the group consisting of ionic complexing; electrostatic complexing; chelation; hydrogen bonding; ion-dipole; dipole/dipole; Van Der Waals forces; and any combination thereof.
Such bonding, via one or more metal cations, e.g., Na.sup.+, of the phyllosilicate sharing electrons with one or two electronegative atoms of one or two electrostatic ends of C.sub.6 + alkyl or aromatic ring-containing intercalant molecules, on inner surfaces of one or both adjacent phyllosilicate platelets surprisingly provides rigid intercalant molecules extending upwardly from the phyllosilicate platelet surfaces, and increases the interlayer spacing between adjacent silicate platelets or other layered material at least about 5 .ANG., preferably at least about 10 .ANG., more preferably to at least about 20 .ANG., and most preferably in the range of about 30 .ANG. to about 45 .ANG., while consuming surprisingly few intercalant molecules in relation to the increased basal spacing achieved. The electronegative atoms at a polar end of the intercalant molecules that coordinate to surround the platelet Na.sup.+ ions can be, for example, oxygen, sulfur, nitrogen, halogen, and combinations thereof.
Such intercalated phyllosilicates easily can be exfoliated into individual phyllosilicate platelets before or during admixture with a liquid carrier or solvent, for example, one or more monohydric alcohols, such as methanol, ethanol, propanol, and/or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylene glycol, glycerine and mixtures thereof; aldehydes; ketones; carboxylic acids; amines; amides; and other organic solvents, for delivery of the solvent in a thixotropic composition, or for delivery of any active hydrophobic or hydrophilic organic compound, such as a topically active pharmaceutical, dissolved or dispersed in the carrier or solvent, in a thixotropic composition; or the intercalates and/or exfoliates thereof can be admixed with a polymer or organic monomer compound(s) or composition to increase the viscosity of the organic compound or provide a polymer/intercalate and/or polymer/exfoliate composition to enhance one or more properties of a matrix polymer.